CHEMISTRY TERM 3 STPM Straight chain alkyl groups

CHAPTER 15 HYDROCARBONS

ALKANES
compound containing carbon and hydrogen atoms only.
saturated hydrocarbons
carbon atoms are joined to each other via single covalent bond only.
also called saturated aliphatic hydrocarbons
o higher members of the series have physical properties similar to Branched chain alkyl groups
compounds found in animal fats and plant oils.
GENERAL FORMULA: CnH2n+2 , n 1
All the carbon atoms undergo sp3 hybridisation
Bond angles = 109.5
Example: petrol, kerosene, paraffin wax

Nomenclatures of Straight-chain Alkanes

Nomenclature of Branched-chain Alkanes

1. Find the parent (root) name indicates the longest carbon chain in the molecule.
2. Each branching is given a name and a number indicates the carbon atom in the
parent chain to which the branch is bonded choose the lowest number.

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 Physical Properties of Alkanes
Alkanes are non-polar, thus they are soluble in non-polar solvents like CCl4.
They are, in general, insoluble and less dense than water.

The boiling point of straight-chain alkanes increases with the size of molecule.
This is because the number of electrons in each molecule increases, resulting in
the increased strength of van der Waals'. Thus more energy is required to break
these forces.

For a branched alkane, it is more volatile and its boiling point is lower than its
counterpart with the same number of carbon atoms. This is because they are more
spherical and have a lower surface area. Thus less temporary dipoles can be set up
and the van der Waals' forces are weaker, less energy is required to overcome it.

The density of liquid alkanes increases slightly. The mass of each succeeding
Cycloalkanes
molecule increases but due to the increased strength of van der Waals' forces, the
General formula: CnH2n , n 3
molecules are closer together. This results in higher ratio of mass/volume.
Add prefix cyclo- to the name of the alkane
Branched chain isomers have lower densities than linear chain isomers. This is
because branched chain isomers are less compactly packed compared to the linear
chain isomers.

Reactions of Alkanes
Inertness of Alkanes
Alkanes are saturated and generally unreactive because they are non-polar, hence
they are unattractive towards nucleophiles and electrophiles.

Halogenation
Structural Isomerism in Alkanes and cis-trans Isomerism in Cycloalkanes
Alkanes undergo halogenation via free-radical substitution. Hydrogen atoms in
1. Draw all possible isomers for alkane with molecular formula C6H14.
the molecule are gradually substituted by halogen atoms.
2. How many primary, secondary, tertiary and quaternary carbon and hydrogen
Reagent : Chlorine gas, Cl2 or bromine gas, Br 2
atoms are there in 2,2-dimethylpropane?
Condition : The presence of ultraviolet(UV) light or sunlight
Product : Halogenoalkanes (alkanes with halogens)

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 Extent of substitution depends on relative amount of methane and chlorine
present.

Mechanism of free-radical substitution:

o Step 1: Initiation step
The reaction is initiated by the homolytic fission of chlorine molecule in
the presence of UV light, forming chlorine free radicals.

o Step 2: Propagation step

The free radicals then attack the methane molecules, leading to a chain
reaction.

o Step 3: Termination step

The reaction ends with the free radicals joining up with each other.

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 Fractional Distillation of Crude Oil

Oxidation (Combustion)
Alkanes undergo complete combustion under excess oxygen gas to give carbon
dioxide and water.

In general,

Larger alkanes are more difficult to ignite. This is because alkanes only burn in
the gaseous state and larger alkanes have stronger van der Waals' forces that hold
them together. Therefore more energy is required to vaporise it.
When the supply of oxygen is limited, alkanes undergo incomplete combustion. Cracking
The possible products are carbon monoxide, carbon and water.
For example,

Quick Check 15.4

10 cm3 of a gaseous hydrocarbon requires 50 cm3 of oxygen for complete combustion to
produce 30 cm3 of CO2. Calculate the molecular formula of the hydrocarbon.

Crude Oil

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Air Pollution Catalytic Converter

ALKENES

Nomenclature of Straight-chain Alkenes

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 Dienes, Trienes and Polyenes

Nomenclature of Branched-chain Alkenes

Structural and cis-trans Isomerism in Alkenes

Example:

Example:

Cycloalkenes

Physical Properties of the Alkenes

Example:

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Reactions of Alkene 2. Halogenation
Unlike alkanes, alkenes are more reactive because they are unsaturated and
contain a C=C bond. A C=C bond contains a bond and a bond. A bond is a
region of high density of electron which is open to attack by electrophiles.
Alkenes mainly undergo electrophilic addition. An electrophilic addition
reaction is the addition of an electrophile across the C=C bond.
Mechanism of electrophilic addition:
o The electronegativity difference in an electrophile, say, XY causes the
molecule to be polar. Therefore it carries a + and - end. The + end of
the molecule behaves as an electrophile.
o The + end is attracted to the bond, a region with high electron
density. As it approaches the bond, the electrons in the X-Y bond are
repelled further and further to the Y atom.
o Eventually the electrons are donated to Y, forming Y ion. The X atom 3. Addition of Hydrogen Halides
forms a single bond with carbon. The electrons needed for this bonding
come from the bond. As a result, the adjacent carbon atom will carry a
positive charge because it has lost its electron to the C-X bond.
o The carbon-containing species which carries a positive charge is called
carbocation. The carbocation is attracted to the negative Y ion. These
two particles eventually bond together via a co-ordinate bond.

Electrophilic Addition
1. Hydrogenation

The addition of unsymmetrical alkenes follows Markovnikov's rule:

In the addition of H-X to a C=C bond of an unsymmetrical alkene, the
hydrogen atom attaches itself to the carbon atom that holds the greatest
number of hydrogen atoms.

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 Carbocation is formed as an intermediate when the electrophile bonds with the
carbon atom.

tertiary carbocation is the most stable

Therefore, if the electrophile is bonded in such a way that a tertiary carbocation is
produced, the stability of the intermediate formed can be increased. This can only
happen if the hydrogen attaches itself with the carbon with most hydrogen atom.

Example:

5. Addition of bromine water

4. Addition of water

5. Addition of Concentrated Sulphuric Acid

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Oxidation of Alkenes
1. Mild Oxidation

3. With Oxygen

2. Vigorous Oxidation

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Ozonolysis Importance of Ethene in Industry

ARENES
Aromatic hydrocarbons with general formula CnH2n-6 , n 6
First member: benzene, C6H6
Does not undergo addition reaction, only can undergo substitution reaction

Nomenclature of Arenes

Polymerisation of Alkenes

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 Structural Isomerism in Arenes

Physical Properties of Benzene

Examples:

Reactions of Benzene
Benzene ring is stable main reaction is substitution
Inert towards oxidising agents
Due to high electron density of the ring, readily attached by electrophiles
Undergo electrophilic substitution

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1. Nitration of Benzene

Mechanism:

Mechanism:

3. Alkylation

2. Halogenation

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Mechanism:

5. Sulphonation

Mechanism:
4. Acylation

Mechanism:

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6. Hydrogenation Example:

Substituent Effect
When a substituted benzene, C6H6Y, undergoes further substitution, the
substituted group (Y) originally in the substituted compound will influence the
rate and location of attack on the benzene ring of the incoming electrophile. 7. Oxidation of Benzene
Y can be ring-activating group or ring-deactivating group Benzene is very stable towards oxidising agents due to the stability of the benzene
molecule containing the ring of delocalised electrons.
ring-activating group ring-deactivating group Benzene burns in air with a sooty smoky flame due to high carbon content.
Electron donors, make benzene ring Electron acceptors, make benzene Chemical equation:
more reactive ring less reactive
Saturated groups Unsaturated groups
Ortho or para directing Meta directing Reactions of Alkylbenzene
Examples: Examples:

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Reactions Involving the Benzene Ring 3. Other electrophilic substitution reactions
Electrophilic substitution
Alkylbenzene is more reactive than benzene (alkyl group - ring-activating groups)

1. Nitration

2. Halogenation Reactions Involving the Side Chain

1. Halogenation

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2. Oxidation

Uses of Arenes

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